Certain benzoyl chloride phenylhydrazones as insecticides and miticides

ABSTRACT

Certain benzoyl chloride phenylhydrazones have been found to be active against insects and mites. The benzoyl ring and the phenylhydrazone ring can be substituted with a halogen atom, a nitro group, or an alkyl group of from 1 to 6 carbon atoms, inclusive. A new class of pentahalobenzoyl chloride phenylhydrazones is described, particularly pentafluorobenzoyl chloride phenylhydrazones. The compounds are prepared by reacting a benzoic acid phenylhydrazide with phosphorus pentachloride to obtain a benzoyl chloride (dichlorophosphinyl) phenylhydrazone that is reacted with phenol to produce the desired benzoyl chloride phenylhydrazones. Certain of the compounds can be prepared by direct chlorination of a benzaldehyde phenylhydrazone. Methods of use and composition are described.

United States Patent .1191

Kaugars et al.

[451 Apr. 22, 1975 CERTAIN BENZOYL CHLORIDE II-IENYLIIYDRAZONES AS INSECTICIDES AND MITICIDES [75] Inventors: Girts Kaugars, Cooper Township.

Kalamazoo County; Edwin G. Gemrich, II, Richland Township, Kalamazoo County. both of Mich.

[73] Assignee: The Upjohn Company, Kalamazoo.

Mich.

[22] Filed: Nov. 26, I968 [21] Appl. No.: 779,25l

Related US. Application Data [63] Continuation-impart of Ser. No. 709.943. March 4.

1968. abandoned.

[52] US. Cl 424/327; 260/566 B; 71/70 [51] Int. Cl A0ln 9/20 [58] Field of Search 424/327; 260/569, 566 B.

[56] References Cited UNITED STATES PATENTS 3,235,447 2/1968 Urbschat ct al. 424/327 Primary E.\'aminerV. D. Turner Attorney, Agent, or F [rm-Roman Saliwanchik; Carl A. Randles. Jr.

[57] ABSTRACT Certain benzoyl chloride phenylhydrazones have been found to be active against insects and mites. The benzoyl ring and the phenylhydrazone ring can be substituted with a halogenatom. a nitro group, or an alkyl group of from 1 to 6 carbon atoms, inclusive. A new class of pentahalobenzoyl chloride phenylhydrazones is described, particularly pentafluorobenzoyl chloride phenylhydrazones. The compounds are prepared by reacting a benzoic acid phenylhydrazide with phosphorus pentachloride to obtain a benzoyl chloride (dichlorophosphinyl) phenylhydrazone that is reacted with phenol to produce the desired benzoyl chloride phenylhydrazones. Certain of the compounds can be prepared by direct chlorination of a benzaldehyde phenylhydrazone. Methods of use and composition are described.

60 Claims, N0 Drawings SUMMARY OF THE INVENTION This invention pertains to a new method of combating pestiferous insects and mites, new insecticidal and miticidal compositions, and new chemical compounds. The invention is more particularly directed to a new method of combating insects and mites using certain benzoyl chloride phenylhydrazones, to new insecticidal and initicidal compositions comprising the certain benzoyl chloride phenylhydrazones, and to new pentahalo benzoyl chloride phenylhydrazones.

The certain insecticidal and miticidal benzoyl chloride phenylhydrazones of this invention have the general structural formula ClH wherein X is halogen, nitro, and alkyl of from 1 to 6 carbon atoms, inclusive; Y is alkyl of from I to 6 carbon atoms, inclusive, halogen. and nitro; n is an integer from O to 5, inclusive; and m is an integer from O to 3, inclusive, the sum of n+m being not more than 6, the sum of carbon atoms in alkyl substituents being not more than 15, and there may be no more than one nitro group in the molecule.

DETAILED DESCRIPTION OF THE INVENTION Among the benzoyl chloride phenylhydrazones of Formula I, the specific compounds benzoyl chloride phenylhydrazone itself, p-chlorobenzoyl chloride phenylhydrazone. benzoyl chloride (p-nitrophenyl)hydrazone, p-chlorobenzoyl chloride (p-bromophenyl)hydrazone, benzoyl chloride (p-chlorophenyl)hydrazone, and benzoyl chloride (2,4,6-trichlorophenyl)hydrazone are known. Benzoyl chloride (2,4-dinitrophenyl)- hydrazone is also a known compound, but it is relatively inactive in comparison with the other known benzoyl chloride phenylhydrazones and thenew benzoyl chloride phenylhydrazones of this invention.

One embodiment of this invention involves new pentahalobenzoyl chloride phenylhydrazones having the general structural formula wherein X is halogenand Y is hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, halogen, or nitro. Surprisingly, these new pentahalobenzyl chloride phenylhydrazones are effective insecticidal and miticidal agents like the above-named, effective, known compounds. Particularly surprising is the fact that pentafluorobenzoyl chloride phenylhydrazone is an out- 5 standing insecticidal and miticidal agent.

The insecticidal and miticidal benzoyl chloride phenylhydrazones of this invention are readily prepared by reacting a selected benzoic acid phenylhydrazide with phosphorus pentachloride, reacting the resulting, corresponding benzoyl chloride (dichlorophosphinyl)phenylhydrazone with phenol, and recovering the desired benzoyl chloride phenylhydrazone. The process can be represented as follows:

ll'l rmm 30 C -N-N Step 1.

(:1 (Y) (i N N 1 p eno Cl -F =0 (o L I Step 2 crH mm l.N l

I n l Step 1. of the foregoing process proceeds when the benzoic acid phenylhydrazide starting compound and the phosphorus pentachloride are mixed in the presence of a reaction medium at a temperature in the range of about 10 C. up to about the boiling point of the reaction medium, although higher and lower temperatures can be used. The reaction rate will be decreased at low temperatures, and a pressure vessel would be needed to effect reaction temperatures above the boiling point at atmospheric pressure. In accordance with a preferred embodiment, the initial reaction mixture is heated.

Appropriate reaction media include, for example, the chlorinated hydrocarbon solvents, aliphatic or aromatic hydrocarbon solvents, and ethers. Representative specific ones are carbon tetrachloride (preferred), methylene chloride, chloroform, l,2-dichloroethylene,

benzene, toluene. technical hexane. diethyl ether, and dioxane.

The process can be practiced without isolating the benzoyl chloride (dichlorophosphinyl)phenylhydrazone intermediate when three equivalents or more of phenol are added to the initial reaction mixture after it has been cooled to about to C. The phenol reacts with the benzoyl chloride (dichlorophosphiny1)- phenylhydrazone intermediate to produce triphenyl phosphate, and the desired benzoyl chloride phenylhydrazone is then recovered and purified by conventional methods. The solvent medium is removed by, e.g., evaporation, and then by mechanically separating the product, e.g.. filtration from the residual triphenyl phosphate or by chromatogrphic techniques. The compound is purified by recrystallization.

The benzoic acid phenylhydrazide starting compounds are known or can be readily prepared by known methods. According to one method a benzoyl chloride is reacted with a phenylhydrazine as described by J. Hausknecht, Chem. Ber. 22, p. 324 (1889), and E. Bamberger and W. Pemsel, Chem. Ber. 36, p. 359 (1903). Another method is described in US. Pat. No. 2,912,461, issued Nov. 10, 1959, that utilizes a benzoate ester and a phenylhydrazine. Still another method described by W. Autenrieth and G. Thomae, Chem. Ber. 57, p. 423 (1924) reacts a benzoic acid anhydride with a phenylhydrazine to produce the corresponding benzoic acid phenylhydrazide. Preparations 1 through XVlll hereinafter illustrate conventional methods for making benzoic acid phenylhydrazide starting compounds.

The insecticidal and miticidal benzoyl chloride phenylhydrazones of this invention (compounds according to Formula 1) can also be prepared by chlorinating a benzaldehyde phenylhydrazone. Chlorination of a benzaldehyde phenylhydrazone can be accomplished as described by J. E. Humphries, H. Humble and R. Evans, J. Chem. Soc. 127, p. 1304 (1925). But chlorination is of limited usefulness when the starting benzaldehyde phenylhydrazone has unsubstituted active sites that will yield to chlorination at positions on the phenylhydrazone nucleus that might want to be avoided in a particular instance. Direct chlorination of benzaldehyde phenylhydrazone is an effective way of producing benzoyl chloride (2,4.6-trichlorophenyl)hydrazone.

Still another method described by L. A. Jones, C. K. Hancock, and R. B. Seligman, J. Org. Chem. 26, p. 228 (1961) can be used. The described method utilized a,a,a-trichlorotoluene and 2,4-dinitrophenylhydrazine to produce benzoyl chloride (2,4-dinitrophenyl)hydrazone. Active compounds of this invention can be prepared in the same manner.

Preparation 1 3,4Dichlorobenzoic acid phenylhydrazide A mixture consisting of 71.8 g. (0.35 mole) methyl 3,4-dichlorobenzoate, 37.9 g. (0.35 mole) phenylhydrazine, 21.6 g. (0.40 mole) sodium methoxide, and 175 ml. methanol was heated at the reflux temperature for 22 hrs. After cooling the reaction mixture to about 25 C., it was poured into 500 ml. water. The aqueous mixture was filtered and the solids that collected on the filter were dissolved in 500 ml. ethanol. Refrigeration caused crystals to form which were recovered by filtration. There was thus obtained 3,4-dichlorobenzoic acid Analysis:

C alc'd for C i-1 C l N O:

C. 55.53; H, 3.59; C1. 2522: N. 9.97. Found: C, 55.87; H, 3.82; C1, 2510; N. 9.85.

Preparation ll Benzoic acid (2.5-dichlorophenyl)hydrazide Preparation 11 Benzoic acid (2,5-dichlorophenyl)hydrazide A mixture consisting of 17.7 g. (0.10 mole) 2.5-dichlorophenylhydrazine, 100 ml. benzene, and 22.6 g. (0.10 mole) benzoic anhydride was heated at the reflux temperature for 1% hrs. After cooling the reaction mixture to about 25 C., it was filtered. The filtrate was evaporated to dryness, and the residue was combined with solids on the filter before dispersing the solids in 700 ml. water basified with 50% aqueous sodium hydroxide to slight alkalinity. The thus washed solids were recovered on a filter, washed with more water, and recrystallized from 225 ml. 95% ethanol. There was thus obtained 23.1 g. (82.2% yield) benzoic acid (2,5-dichlorophenyl)hydrazide having a melting point of 160.5 to l61.5 C. An analytical sample melting at 161 to 162 C. was obtained by recrystallization from 95% ethanol.

Calcd for C H ChNO:

C. 55.53. H. 3.59; CI, Found: C. 55.57; H. 3.91; CI,

Preparation 111 p-Fluorobenzoic acid phenylhydrazide phenylhydrazide melting at 177 to 179 C. was ob-' tained by recrystallizing once from a mixture of ethyl acetate and Skellysolve B (essentially a mixture of isomeric hexanes boiling in the range of 146 to 156 F.), and once from aqueous ethanol.

Analysis:

Calcd for c H FN O:

C. 67.81; H. 4.82: Found: C. 68.28; H,

Preparation 1V p-Chlorobenzoic acid (p-bromophenyl)hydrazide A mixture consisting of 44.7 g. (0.20 mole) p-bromo- 15.5 g. p-chlorobenzoic acid (p-bromophenyhhydra Prepartion Vll p-lsopropylbenzoic acid phenylhydrazide To a solution of 35.0 g. (0.323 mole) phenylhydrazine in 300 ml. pyridine, cooled to about 50 to 8 C., was added 54.8 g. (0.30 mole) p-isopropylbenzoyl chloride. This reaction mixture was set aside for 37 hrs. at about 25 C. The mixture was then poured into 1500 ml. ice-water and the solids that separated were coli tiavingla p 2 2 lected on a filter and washed with water. After recrysy Samp 6 me K was) tame tallization from 850 ml. ethanol. there was obtained after two recrysta111zat1ons from ethyl acetate. 64.7 g (843% yield) of p isopropylbenzoic acid phenylhydrazide melting at 198 to 201 C. An analyti- H cal sample melting at 200.5 to 202.5 C. was obtained Analysis: after two recrystallizations from ethanol.

d L 654742311. 3.10. Br. 24.54; (71. 10119; N. 11.61. Found: C. 48.09; H. 3.20: Br. 24.40; Cl. 10.44; N. 8.56.

Analysis: C alc'd for C H MO:

C. 75.56; H. 7.13; N 11.02. Preparation V Found: C. 75.59; H. 7.14; N. 10.78.

m-Chlorobenzoic acid phenylhydrazide To a solution of 21.63 g. (0.02 mole) phenylhydra- P zinc in 250 m1. diethyl ether was added 125 ml. (0.20 f Vm mole) butyl lithium (1.6M in hexane). The addition BBHZOIC d 0-t01ylhydraz1de was effected at 6() to 70 C. The resulting suspen- To 31773 (020 mole) of o tolylhydmzine hydm was warmed to and (0-20 mole) chloride and 45 25 g (0 "0 mole) of benzoic anhydride chlorobenzoyl chloride in 35 ml. ether was added dropin 25 m1 f benzene was added 350 (O25 mole) wtise. This reaci1tiotnhmixtugeflwas:gured at drogmtleni h of triethylanfiine, and the suspension was refluxed for a a e e er was e one hour. A ter cooling to about 25C.. the solids were ether w retnoved y Y Pf and the resldue w filtered. The filtrate was evaporated to dryness and the comblnedwlth e seml-solld left 31 the deeamatlonresidue was combined with solids on the filter before d ggg l stlllds elg ilp fil tz 200 rf- S l 35 dispersgng 111'; sglids in water basified with 50% aquearl m wa er was a e e was e S ous so ium y roxide to slight alkalinity. The thus were collected a filter, washed ig s l i washed solids were recovered on a filter, washed with The dried solids were recrystallized mm m 9 a more water, and recrystallized from 400 ml. of about mixture ofskenysolve B and benzene (1 to g e 190 1:1 ethyl acetate-ethanol. There was thus obtained 30.0 g g g acild p y yf e at 40 g. (64.4% yield) of benzoic acid o-tolylhydrazide hav- 5 t nana tica sam e avm ame 1n f O o point :t 156 to 157.5 C was obtained by a recrystalli 5: S mis 32 g cg $12.22: 3:22! zation from a m ture of benzene and ethanol (about crystallization from ethanol and then from ethyl ace- 100:1) and a final recrystallization from benzene. m

Analysis: Analysis:

Calcd for c H ClN- Oz Calcd for C H N O:

C. 63.29; H. 4.50; Cl, 14.37; N. 11.36. C, 74.31; H. 6.24; N, 12.38. Found: C. 63.34; H. 4.41; C1, 14.35; N, 11.55. Found: C. 74.22; H. 6 18;N, 12.66.

Preparation V1 Preparation 1X o-Chlorobenzoic' acid phenylhydrazide 2,4-Dichlorobenz oic acid phenylhydrazide Following the procedure of Prepar io but SubSti- Following the procedure of Preparation Vll, but subtuting methyl 3,4-dichlorobenzoat:i witlrill meghyl 6- :)tituting 2,4igichliorobertilzoyl chloride for p-isgprogydlchlorobenzoate, there was prepare o-c oro enzolc enzoy c ori e, t ere was prepare acid phenylhydrazide having a melting point of 154.5 dichlorobenzoic acid phenylhydrazide having a melting to 155.5 C. point of 181 to 182 C.

Analysis: Analysis:

Calcd for c..H,.c1N..0; Calcd for C13H|QCI N2OZ c 63.29; 11, 4.50;c1. 14.37; N. 11.36 c. 55.53; 11. 3.59; (:1. 25.22; N. 9.97. Found: C: 63.60; H, 4.59; Cl, 14.50; N. 11.19 Found: C; 55.96. H, 3.85; CI, 25.19; N, 9.78.

Preparation X m-Toluic acid phenylhydrazide Following the procedure of Preparation V11. but substituting m-toluoyl chloride for p-isopropylbenzoyl chloride, there was prepared m-toluic acid phenylhydrazide having a melting point of 162 to 163 C. 1

Analysis:

Calcd for C H N O:

C. 74.31: H. 6.24. N. 12.38. Found: C, 74.36; H. 6.21; N. 12.53.

Preparation XI Benzoic acid (p-chlorophenyl)hydrazide Following the procedure of Preparation V111. but substituting p-chlorophenylhydrazine hydrochloride for o-tolylhydrazine hydrochloride, there was prepared benzoic acid (p-chlorophenyl)-hydrazide having a melting point of 153.5 to 154.5 C.

Preparation XIV 3-Methyl-4-nitrobenzoic acid phenylhydrazide Analysis:

Calcd for C H N O C. 61.98; H. 4.83; N. 15.49. Found: C. 61.46; H. 4.90; N. 15.52.

Preparation XV 2,5-Dimethylbenzoic acid phenylhydrazide Following the procedure of Preparation VII, but substituting 2.5-dimethylbenzoyl chloride for p-isopropylbenzoyl chloride, there was prepared 2,5- dimethylbenzoic acid phenylhydrazide having a melt- Ammiv ing point of 208 to 209 C.

Calc'd for (.,;,H ClN- C. 63.29; H. 4.50; C1. 14.37; N. 11.36. Found: C. 63.03; H. 4.63; C1. 14.16; N. 11.26.

Analysis:

Calc'd for C -,H ;N- .O: C. 74.97; H. 6.71; N. 11.66. Preparation XI] Found: C. 74.56: H. 6.66: N. 1 1.56.

p-lodobenzoic acid phenylhydrazide A solution of 44.7 g (0.168 mole) of p-iodobenzoyl chloride in 100 m1. of dioxane was added to 18.2 g. Prepa'am" XVI (0.168 mole) of phenylhydrazine dissolved in 250 ml. 2-Chloro-4-nitrobenzoic acid phenylhydrazide of pyridine at 5 to 15 C. The resulting suspension was Followin l O g the procedure of Preparation XII, but submrred about 3 days poured hters stituting 2-chloro-4-nitrobenzoyl chloride for pof water. the sol1ds were filtered and washed with wa- 40 iodobenzoyl chloride, there was prepared 2-ch1oro- 4- ter. d11ute aqueous hydrochloric acld and then again nltrobenzoic acid phenylhydrazide having a melting wlth water. The product thus obtained was crystallized t f 179 t 180 C from ethanol to give 40.0 g. (70.9% yield) of ppom o 0 iodobenzoic acid phenylhydrazide having a melting point of 210 to 211C.

Analysis:

C alc'd for C H ClN O C. 53.53; H. 3.45; CI. 12.15; N. 14.41. Analysis: Found: C. 53.46; H. 3.60; C1. 12.00: N. 14.05.

Calcd for CHHHINQO:

c. 46.47. H 3.28; 1. 37.53; N. 8.29. Found: C. 46.34; H. 3.44; 1. 37.53; N. 8.32.

Preparation XVII Pentafluorobenzoic acid phenylhydrazide Preparation X111 F u h d fP v b b o owmgt eproce ureo reparation ut su 3s'Dlmethylbenzo'c dud phenylhydrazlde stituting pentafluorobenzyl chloride for p-isopropyl- Following the procedure of Preparation VII, but subbenzoyl chloride, there was prepared pentafluorobenstituting 3,5-dimethylbenzoyl chloride for p-isopropylzoic acid phenylhydrazide having a melting point of benzoyl chloride. there was prepared 3,5- l52 5 t 153 5 C. dimethylbenzoic acid phenylhydrazide having a melting point of 197.5 to 198.5 C.

Analysis:

Calcd for C H F N- O: A 1y C. 51.66; H. 2.34; N, 9.27. j for CHHMMO. Found: C. 51.84; H. 2.43; N. 9.27.

C. 74.97; H. 6.71; N 11.66 Found: C. 74.92; H, 6.63; N 11.59

phenylhydrazide having a melting point of 200 to 201 C.

Analysis:

Calcd for C H BrN-p:

(153.63; H. 3.81; Br. Found: C. 53.71: H. 3.85; Br.

The following examples are illustrative of the process and products of the present invention. but are not to be construed as limiting.

EXAMPLE 1 Preparation of p-nitrobenzoyl chloride phenylhydrazone A quantity (12.86 g.. 0.05 mole) of p-nitrobenzoic acid phenylhydrazide. prepared according to the method described by .l. Hausknecht. Chem. Ber.'22. p. 324 (1889). was added to a suspension of 10.41 g. (0.05 mole) phosphorus pentachloride in 75 ml. carbon tetrachloride, and the resulting suspension was heated to the reflux temperature. Heating at the reflux temperature was continued until evolution of hydrogen chloride gas ceased. After cooling the reaction mixture to about 25 C.. it was poured into an ice-cold suspension of 15.5 g. (0.17 mole) of phenol in 50 ml. carbon tetrachloride. When the reaction between the phenol and the p-nitrobenzyl chloride (dichlorophosphinyl)- phenylhydrazone intermediate was completed. the carbon tetrachloride solvent and other volatile components were removed by evaporation under reduced pressure at 30 C. The resulting suspension of pnitrobenzoyl chloride phenylhydrazone in triphenyl phosphate was filtered and the filter cake comprising the p-nitrobenzoyl chloride phenylhydrazone was washed with 100 ml. carbon tetrachloride. 50 ml. methanol, and 50 ml. ether. The solid on the filter was recrystallized from a solvent mixture consisting of 100 ml. benzene and 300 ml. naphtha (boiling range 203 to 212 F.). There was thus obtained 4.10 g. of pnitrobenzoyl chloride phenylhydrazone having a melting point of 156 to 157.5 C. A second recrystallization from a mixture of benzene and Skellysolve C gave the compound melting at 157 to l58.5 C.

Analysis:

Calc'd for C...H...C1N..0.

, C. 56.6.;1-1. 3.66; CI. 12.86: N. 15.24.

Found: C. 56.40. H. 3.43; CI. 13.18; N. 14.81.

EXAMPLE 2 Preparation of 3,4-dichlorobenzoyl chloride phenylhydrazone Following the same procedure as Example 1, but substituting 28.1 1 g. (0. mole)J3,4-dichlorobenzoic acid phenylhydrazide (prepared as in Preparation 1, above), for the p-nitrobenzoic acid phenylhydrazide, and using Analysis:

Calcd for C H Cl N z C. 52.12111. 3.03; Cl. 35.50; N. 9.35. Found: C. 52.38: H. 3.07; Cl. 35.96; N. 9.02.

EXAMPLE 3 Preparation of benzoyl chloride (2,5-dichlorophenyl)hydrazone A quantity (16.87 g.. 0.06 mole) benzoic acid (2,5-dichlorophenyl)hydrazide (Preparation 11. above) was added to a solution of 12.50 g. (0.06 mole) phosphorus pentachloride in 50 ml. carbon tetrachloride.

and the resulting suspension was allowed to react at 25 C. until evolution of hydrogen chloride gas slowed. The reaction mixture was then heated at the reflux temperature for 15 minutes, chilled in ice, and 17.8 g. (0.19 mole) phenol in ml. carbon tetrachloride was added. After the reaction was completed, the carbon tetrachloride was removed by evaporation under reduced pressure at 30 to 32 C. The resulting suspension was filtered. and the filter cake was washed with 50 ml. cold methanol. Two recrystallizations from Skellysolve B gave benzoyl chloride (2.5-dichlorophenyl)hydrazone melting at 845 to 86 C.

Analysis:

Calcd for C H Cl N C. 52.12; H. 3.03; N. 9.35. Found; C. 52.59: H. 3.16; N. 9.27.

Following the procedure of Example 3. but substituting 22.63 g. (0.10 mole) p-toluic acid phenylhydrazide [prepared as described by Ponzio and Charrier, Gazz. chim. ital. 38 I, p. 528 (1908)] for the benzoic acid 2,S-dichlorophenylhydrazide and using 21.5 g. (0.013 mole) phosphorus pentachloride in m1. carbon tetrachloride, there was obtained p-toluoyl chloride (dichlorophosphinyl)phenylhydrazone which was reacted with 32.0 g (0.34 mole) phenol in 50 ml. carbon tetrachloride to produce p-toluoyl chloride phenylhydrazone. Two recrystallizations from a mixture of benzene and Skellysolve B gave the compound with a melting point of 133 to 134.5 C.

Analysis:

Calcd for C H CIN- C. 68.71; H. 5.35; C1. 14.49; N. 11.45. Found: C. 69.03; H. 5.27; CI. 14.88 N 11 37.

EXAMPLE Preparation of p-fluorobenzoyl chloride phenylhydrazone Analysis:

Calcd for C HwClFN C. 62.78: H. 4.05; Cl. 14.26; F. 7.64; N. 11.27. Found: C. 62.78: H. 4.051Cl. 14.01. F. 7.38: N. 10.87.

EXAMPLE 6 Preparation of p-chlorobenzoyl chloride (p-bromophenyl )hydrazone A quantity (5.50 g.. 0.0264 mole) phosphorus pentachloride was added to a suspension of 8.14 g. (0.0250 mole) p-chlorobenzoic acid (p-bromophenyl)hydrazide (Preparation 1V. above) in 50 ml. carbon tetrachloride and the mixture was heated at the reflux temperature until evolution of hydrogen chloride gas ceased. After cooling the reaction mixture in ice. 8.0 g. (0.085 mole) phenol in ml. carbon tetrachloride was added. After the reaction was completed and evolution of hydrogen chloride gas has ceased, the mixture was filtered and the filter cake was washed with ml. Skellysolve B. The solids on the filter were dissolved in 20 ml. ethyl acetate. and the solution was brought to a volume of 90 ml. by the addition of Skellysolve B. The diluted solution was filtered and set aside to crystallize. There was thus obtained 5.50 g. (64.0% yield) of pchlorobenzoyl chloride (p-bromophenyl)hydrazone having a melting point of 142 to l43.5 C.

Analysis:

Calcd for C I-1 BrCl N C,45.38; H, 2.64; Br. 23.23; Cl, 20. Found: C,45.37; H, 2.82; Br, 23.39; Cl, 20.

EXAMPLE 7 Preparation of p-chlorobenzoyl chloride (2 .4.6-trichlorophenyl )hydrazone To a suspension of 6.92 g. (0.030 mole) of pchlorobenzaldehyde phenylhydrazone in 100 ml. glacial acetic acid was added 7.0 ml. (0.154 mole) chlorine. The mixture was diluted with another 100 ml. gla- 7r yield) of p-chlorobenzoyl chloride (2,4,6-trichlorophenyl)hydrazone having a melting'point of 122.5 to 124.5 C. An analytical sample having a melting point of 123 to 124 C. was obtained by two recrystallizations from a mixture of Skellysolve B and benzene.

Analysis:

C alcd for C -,H C l N C. 42.37: H. 1.91: CI. 48.11: N. 7.60. Found: C. 42.75: H. 2.21; Cl. 48.15; N. 7.

EXAMPLE 8 Preparation 'of benzoyl chloride (2,4.6-trichlorophenyl)hydrazone Following the procedure of Example 7. but substituting carbon tetrachloride for glacial acetic acid as solvent. substituting benzaldehyde phenylhydrazone for p-chlorobenzaldehyde phenylhydrazone, and cooling the reaction mixture in an ice bath during the addition of chlorine and subsequently refluxing for one hour, there was prepared benzoyl chloride (2,4,6-trichlorophenyl)hydrazone having a melting point of 93 t 94.5 C.

Found: C. 47.03;

EXAMPLE 9 Preparation of m-chlorobenzoyl chloride phenylhydrazone Analysis:

Calc'd for C H Cl N- z C. 58.89; H. 3.80; CI, 26.74; N. 10.57. Found: C. 59.40; H. 4.00; CI. 26.75; N. 10.57.

EXAMPLE 10 Preparation of p-isopropylbenzoyl chloride phenylhydrazone Following the procedure of Example 1, but substituting p-isopropylbenzoic acid phenylhydrazide (Preparation Vll. above) for p-nitrobenzoic acid phenylhydrazide. there was prepared p-isopropylbenzoyl chloride phenylhydrazone having a melting point of lO0.5 to 102 C.

Analysis:

Calcd for C H ClN z C. 70.45; H. 6.28; CI. 13.00; N. 10.27. Found: C, 70.59; H 9

t 6.3 ;CI. 13.00; N. 9.80.

EXAMPLE ll Preparation of otoluoyl chloride phenylhydrazone Following the procedure of Example l3 below. but substituting o-toluic acid phenylhydrazide for ochlorobenzoic acid phenylhydrazide. there was prepared o-toluoyl chloride phenylhydrazone.

EXAMPLE 12 Preparation of 2.4-dichlorobenzoyl chloride phenylhydrazone Following the procedure of Example I. but substituting 2.4-dichlorobenzoic acid phenylhydrazide (Preparation lX. above) for p-nitrobenzoic acid phenylhydrazide. there was prepared 2.4-dichlorobenzoyl chloride phenylhydrazone having a melting point of 88.5 to 895 C.

Analysis:

Calcd for C ,;,H,,Cl N

C. 52.l2; H. 3.03: Cl. 35.50:

N. 9.35. Found: C. 52.29; H. 3.06: Cl. 35.69: N. 8

EXAMPLE 13 Preparation of o-chlorobenzoyl chloride phenylhydrazone Analysis:

Calc'd for CmHmClgNgl C. 58.89 H

LII

there was prepared m -toluoyl chloride phenylhydrazone having a melting point of 66 to 67 C.

Analysis:

C alcd for C H CIN C. 68.71; H. 5.35; CI. l4.49; N. ll.45. Found: C. 68.84; H. 5.4l; Cl. 14.45; N. l l.l7.

EXAMPLE 16 Preparation of benzoyl chloride (p-chlorophenyl )hydrazone Following the procedure of Example I. but substituting benzoic acid (p-chlorophenyl)hydrazide (Preparation XI. above) for p-nitrobenzoic acid phenylhydrazide. there was prepared benzoyl chloride (p-chlorophenyl)hydrazone having a melting point of 107 to l08.5 C.

ing p-bromobenzoic acid phenylhydrazide (Preparation XVIII. above) for p-nitrobenzoic acid phenylhydrazide. there was prepared p-bromobenzoyl chloride phenylhydrazone having a melting point of l5l.5 to 153C.

3.80: CI. 26.74: N. l0.57. Found: C. 58.68; H. 3.87; Cl. 26.50: N. l().5(). Analysis:

45 Calcd for C H BrClN z C. 50.43: H. 3.26; Br. 25.8l; Cl. HA5; N. 9.05. Fo d: C. 50.05; H. 3.23; B 25.77; Cl. ll.70: N. 9.l6. EXAMPLE l4 Preparation of benzoyl chloride o-tolylhydrazone Following the procedure of Example 13. but substituting benzoic acid o-tolyhydrazide (Preparation Vlll. above) for o-chlorobenzoic acid phenylhydrazide, there was prepared benzoyl chloride o-tolylhydrazone having a melting point of 64.5 to 66 C.

Analysis:

Calc'd for C H ClN C. 68.71: H. 5.35; Cl. 14.49; Found: C. 69.06: H. 5.42; CI. l4.6l;

N. ll.45. N. ll.22

EXAMPLE l5 Preparation of m toluoyl chloride phenylhydrazone Following the procedure of Example 13, but substituting m-toluic acid phenylhydrazide (Preparation X, above) for o-chlorobenzoic acid phenylhydrazide.

EXAMPLE 18 Preparation of benzoyl chloride (p-nitrophenyl )hydrazone Analysis:

Calcd for C ..H...C|N.0

C. 56.63; H. 3.66; CI. i186: N. 15.24. Found: C. 56.76; H. 3.73; CI. 12.90; N. 15.37.

EXAMPLE 19 Preparation of benzoyl chloride (2.4-dibromophenyl)hydrazone Analysis:

Calc'd for C -,H,,Br. .CIN

C. 40.19: H. 2.33; N. 7.21. Found: C. 39.50; H. 2.46; N. 7.16

EXAMPLE 20 Preparation of 2,5-dimethylbenzoyl chloride phenylhydrazone Following the procedure of Example 13, but substituting 2.5-dimethylbenzoic acid phenylhydrazide (Preparation XV, above) for o-chlorobenzoic acid phenylhydrazide, there was prepared 2.5- dimethylbenzoyl chloride phenylhydrazone having a melting point of 48.5 to 49 C.

H. Found: C. 69. .1 H. 5.81; CI. 13.90; N. 10.66.

EXAMPLE 21 Preparation of 2-chloro-4-nitrobenz0yl chloride phenylhydrazone Following the procedure of Example 1, but substituting 2-chloro-4-nitrobenzoic acid phenylhydrazide (Preparation XVl, above) for p-nitrobenzoic acid phenylhydrazide, there was prepared 2-chloro-4- nitrobenzoyl chloride phenylhydrazone having a melting point of 124 to 126 C.

Analysis:

Calc'd for C ;,H,.Cl- ,N:

C. 50.34; H. 2.931Cl, 22.86; N, 13.55. Found: C. 50.22; H, 3.15; Cl, 23.03; N, 13.29.

EXAMPLE 22 Preparation of 2,6-dichlorobenzoyl chloride phenylhydrazone Following the procedure of Example 1, but substituting 2,6-dich1orobenzoic acid phenylhydrazide for pnitrobenzoic acid phenylhydrazide, there was prepared 2,6-dichlorobenzoyl chloride phenylhydrazone.

EXAMPLE 23 Preparation of pentafluorobenzoyl chloride phenylhydrazone Following the procedure of Example 1, but substituting pentafluorobenzoic acid phenylhydrazide (Preparation XVll, above) for p-nitrobenzoic acid phenylhydrazide, there was prepared pentafluorobenzoyl chlorde phenylhydrazone having a melting point of 1 17 to l 18C.

a ;1-1. 1.89; CI. 11.06; N, 8.74. Found: C. 49.03; H. 2.20; C1. 1104; N. 8.91.

EXAMPLE 24 Preparation of 3,4-dimethylbenzoyl chloride phenylhydrazone Following the procedure of Example 13, but substituting 3,4-dimethylbenzoic acid phenylhydrazide for o-chlorobenzoic acid phenylhydrazide, there was prepared 3,4-dimethylbenzoyl chloride phenylhydrazone.

EXAMPLE 25 Preparation of p-iodobenzoyl chloride phenylhydrazone Following the procedure of Example 1, but substituting p-iodobenzoic acid phenylhydrazide (Preparation X11, above) for p-nitrobenzoic acid phenylhydrazide, there was prepared p-iodobenzoyl chloride phenylhydrazone having a melting point of 164 to 165 C.

Analysis:

Calc'd for C H CllN- Found: C. 44.02; H. 2.94;

EXAMPLE 26 Preparation of 3-methyl-4-nitrobenzoyl chloride phenylhydrazone Following the procedure of Example 1, but substituting 3-methyl-4-nitrobenzoic acid phenylhydrazide (Preparation XIV, above) for p-nitrobenzoic acid phenylhydrazide, there was prepared 3-methyl-4- nitrobenzoyl chloride phenylhydrazone having a melting point of 146 to l47.5 C.

Analysis:

Calc'd for C H .C1N;,O

C. 58.04; H. 4.18; Cl. 12.24; N. 14.50. Found: C, 58.06; H. 4.29; CI, 12.41; N. 14.31.

EXAMPLE 27 Preparation of 3,5-dimethylbenzoyl chloride phenylhydrazone Following the procedure of Example 13, but substituting 3,5-dimethylbenzoic acid phenylhydrazide (Preparation X111, above) for o-chlorobenzoic acid on a filter. The filter cake was recrystallized from glacial acetic acid to give 4.9 g. benzoyl chloride (2.4-dichlorophenyl)hydrazone having a melting point at 890 to 905 C.

Analysis:

Calcd for C -,H -,N Cl:

Cl. 13.70: N. 10.83. Found: Cl. 13.74; N. 10.92.

EXAMPLE 28 Following the procedure of Example 1. but substituting p-butylbenzoic acid phenylhydrazide. p-( 1- methylbutyl )benzoic 7 acid phenylhydrazide. phexylbenzoic acid phenylhydrazide. 3 ,4.5- trimethylbenzoic acid phenylhydrazide, 2,4,6-

zone, 2.4,6-triisopropylbenzoyl chloride (3,5- diisopropylphenyl)hydrazone. p-toluoyl chloride (p-ethylphenyl)hydrazone, p-hexylbenzoyl chloride (p-hexylphenyl)hydrazone. 3-chloro-5-methylbenzoyl chloride phenylhydrazone, p-toluoyl chloride (pbromophenyhhyrazone, p-nitrobenzoyl chloride (p-bromophenyl)hydrazone, p-nitrobenzoyl chloride (p-isopropylphenyl)hydrazone. and p-isopropylbenzoyl chloride (2-chloro-4-nitrophenyl)hydrazone. respectively.

EXAMPLE 29 Following the procedure of Example 8. but substituting m-tolualdehyde phenylhydrazone, p-isopropylbenzaldehyde (2,4,6-trichlorophenyl)hydrazone, and benzaldehyde p-tolylhydrazone for benzaldehyde phenylhydrazone, there were prepared m-toluoyl chloride (2,4,6-trichlorophenyl)hydrazone, p-isopropylbenzoyl chloride (2,4,6-trichlorophenyl)hydrazone, and benzoyl chloride (2,6-dichloro-4-methylphenyl)hydrazone. respectively.

EXAMPLE 30 Preparation of benzoyl chloride (2,4-dichlorophenyl )hydrazone A suspension consisting of 6.86 g. (0.035 mole) benzaldehyde phenylhydrazone, 100 ml. glacial acetic acid, and 200 ml. carbon tetrachloride was cooled to C. and 0.11 mole chlorine was introduced while the temperature of the reaction mixture was kept below C. After being set aside for about 16 hrs., the reaction solution was filtered. The filtrate was concentrated by removing most of the carbon tetrachloride under reduced pressure. The concentrate was poured over crushed ice and the solids that formed were collected Analysis:

C alc'd for C H C1 N C. 52.12; H. 3.03; Cl. 35.50: N. 9.35.

H. 2.991cl. 35.69: N. 9.68.

Found: C. 52.27:

The insecticidal and miticidal benzoyl chloride phenylhydrazones of Formula 1 can be used as the pure compounds, such as those described in the Examples, or as technical grade compounds from commercial production; but for practical reasons, the compounds are preferably formulated as insecticidal and miticidal compositions. More particularly, the benzoyl chloride phenylhydrazones are preferably formulated with a diluent carrier. There are many different kinds of diluent carriers useful for preparing insecticidal and miticidal compositions. Dispersible insecticide and miticide carriers are commonly used in the art. Such carriers may or may not include adjuvants such as wetting agents. emulsifying agents. stickers, and other components that indirectly promote efficacy.

For example. pesticidal compositions useful against insects and mites which infest plants can be formulated as dusts, wettable powders. emulsifiable concentrates. aqueous dispersions, solutions. and flowable creams for application to animals and foliage, seeds or other parts of plants. Compositions suitable for root or bole infusion can be made, and granular compositions can be made and applied to soil or on surfaces. Moreover. the benzoyl chloride phenylhydrazones of the invention can be the sole active agent in a composition or other insecticidal, miticidal, fungicidal, virucidal. bactericidal, or synergistic components may be included.

The benzoyl chloride phenylhydrazones can be readily formulated as dusts by grinding a mixture of the compound and a pulverulent carrier in the presence of each other. Grinding is conveniently accomplished in a ball mill, a hammermill. or by air-blast micronization. A suitable ultimate particle size is less than 60 microns. Preferably, 95% of the particles are less than 50 microns, and about are 5 to 20 microns. Dusts of that degree of comminution are conveniently free-flowing and can be applied to animals, inanimate matter, fruit trees. crop plants, and soil so as to effect thorough distribution and coverage. Dusts are particularly adapted for effectively controlling insects and mites over wide areas when applied by airplane. They are also indicated for application to the undersides of plant foliage and to the skin of poultry and hairy animals.

Representative suitable pulverulent carriers include the natural clays such as China, Georgia, Barden, attapulgus, kaolin, and bentonite clays; minerals in their natural forms as they are obtained from the earth such as talc, pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk, rock phosphates and sulfates, calcium carbonates, sulfur, silica and silicates; chemically modified minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium silicate, synthetic magnesium silicate, and colloidal silica; and organic flours such as wood, walnut shell, soybean, cottonseed, and tobacco flours, and free-flowing, hydrophobic starches.

Dusts can also be prepared by dissolving a benzoyl chloride phenylhydrazone in a volatile solvent such as methylene chloride, mixing the solution with a pulverulent carrier and evaporating the solvent.

The proportions of pulverulent carrier and benzoyl chloride phenylhydrazone can vary over a wide range depending upon the insects or mites to be controlled and the conditions of treatment. In general, dust formulations can contain up to about 90% (on a weight basis) of the active ingredient. Dusts having as little as 0.001% of the active ingredient can be used, but a generally preferred porportion is from about 0.50% to about of active ingredient.

The dispersible powder formulations of this invention are prepared by incorporating a surfactant in a dust composition prepared as described above. When about 0.1% to about 12% of a surfactant is incorporated in a dust, the dispersible powder thus obtained is particularly adapted for further admixture with water for spraying on inanimate matter and products, fruit trees, field crops, soil, and livestock. The dispersible powders can be admixed with water to obtain any desired concentration of active ingredient, and the mixture can be applied in amounts sufficient to obtain predetermined rates of application and uniform distribution. With this flexibility in mind, the dispersible powders of the invention can conveniently comprise preferably about 10 to about 80% of active ingredient.

Representative surfactants useful for preparing dispersible powder formulations of this invention inclue alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene-sorbitan monolaurate, alkyl aryl polyether sulfates, alkyl aryl polyether alcohols, alkyl naphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty acids and esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, lignin sulfonates, and the like. The preferred class of surfactants includes blends of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77), blends of polyoxyethylene ethers and oil-soluble sulfonates (Emcol H-400), blends-of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Tritons X-l5l, X-l6l, and X-l71), e.g., about equal parts of sodium kerylbenzene sulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl aryl sulfonates and polyethoxylated vegetable oils (Agrimul N 5). It will be understood, of course, that the sulfate and sulfonate surfactants suggested above will preferably be used in the form of their soluble salts, for example, their sodium salts. All of these surfactants are capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1% or less. The dispersible powder compositions can be formulated with a mixture of surfactants of the types indicated if desired.

A suitable dispersible powder formulation is obtained by blending and milling 327 lbs. of Georgia Clay, 4.5 lbs. of isooctylphenoxy polyethoxy ethanol (Triton X-l00) as a wetting agent, 9 lbs. of a polymerized sodium salt of substituted benzoid long-chain sulfonic acid (Daxad 27) as a dispersing agent, and l 13 lbs. of the active ingredient. The resulting formulation has the following percentage composition (parts herein are by weight unless otherwise specified).

Active ingredient 25% lsooctylphenoxy polyethoxy ethanol 1% Polymerized sodium salt of substituted benzoid long-chain sulfonic acid 2% Georgia Clay 72% This formulation, when dispersed in water at the rate of 10 lbs. per gals., gives a spray formulation containing about 0.3% (3000 ppm) active ingredient which can be applied to insects or mites, plants or other insect or mite habitats, or insect or mite foods to control insects or mites.

If desired, dispersants such as methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, and the like can be included in the dispersible powder formulations of this invention. Adhesive or sticking agents such as vegetable oils, naturally occurring gums, casein, and others can also be included. Corrosion inhibitors such as epichlorohydrin and anti-foaming agents such as stearic acid can also be included.

The insecticidal and miticidal benzoyl chloride phenylhydrazones of this invention can be applied to insects, mites, objects, or situs in aqueous sprays without a solid carrier. Since, however, the compounds themselves are relatively insoluble in water they are preferably dissolved in a suitable inert organic solvent carrier. Advantageously, the solvent carrier is immiscible with water so that an emulsion of the solvent carrier in water can be prepared. 1f, for example, a watermiscible solvent carrier such as ethanol is used the solvent carrier will dissolve in the water and any excess benzoyl chloride phenylhydrazone will be thrown out of solution. In an oil-in-water emulsion, the solvent phase is dispersed in the water phase and the dispersed phase contains the active ingredient. ln this way, uniform distribution of a water insoluble active ingredient is achieved in an aqueous spray. A solvent carrier in which benzoyl chloride phenylhydrazones are high-1y soluble is desirable so that relatively high concentrations of active ingredient can be obtained. Sometimes, one or more solvent carriers with or without a cosolvent can be used in order to obtain concentrated solutions of the active ingredient, the main consideration being to employ a water-immiscible solvent for the active ingredient that will hold the compound in solution over the range of concentrations useful for applying to insects and mites.

The emulsifiable concentrates of the invention are;

prepared, therefore, by dissolving the active ingredient and a surfactant in a substantially water-immiscible solvent carrier (i.e., a solvent carrier which is soluble in water to the extent of less than 2.5% by volume at temperatures of the order of 20 to 30 C.), for example, cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbons such as benzene, toluene and xylene, and high-boiling petroleum hydrocarbons such as kerosene, diesel oil, and the like. If desired, a cosolvent such as methyl ethyl ketone, acetone, isopropanol, and the like can be included with the solvent carrier in order to enhance the solubility of the active ingredient. Aqueous emulsions are then prepared by mixing with water to give any desired concentration of active ingredient. The surfactants'which can be employed in the aqueous emulsions of the invention are those types noted above. Mixtures of surfactants can be employed, if desired.

Advantageously, the concentration of active ingredient in the emulsifiable concentrates can range from about to about 50% by weight, preferably from about to about 40%. A concentrate comprising (by weight) of the compound dissolved in a waterimmiscible solvent of the kind noted above can be admixed with an aqueous medium in the proportions of 13 ml. of concentrate with 1 gal. of medium to give a mixture containing 700 parts of active ingredient per million parts of liquid carrier. Similarly, I qt. of a 20% concentrate mixed with 40 gals. of water provides about 1200 ppm (parts per million) of active ingredient. In the same manner, more concentrated solutions of active ingredient can be prepared.

The concentrate compositions of the invention which are intended for use in the form of aqueous dispersions or emulsions can also comprise a humectant, that is to say, an agent which will delay the drying of the composition in contact with material to which it has been applied. Suitable humectants include glycerol, diethylene glycol, solubilized lignins, such as calcium ligninsulfonate, and the like.

The granular compositions of this invention are convenient for application to soil when persistence is desired. Granulars are readily applied broadcast or by localized, e.g., in-therow applications. The individual granules may be any desired size from to 60 mesh up to 20 to 40 mesh, or even larger. Granulars are prepared by dissolving the active compound in a solvent such as methylene chloride, xylene, or acetone and applying the solution to a quantity of a granulated absorbent carrier. Representative granulated absorbent carriersinclude ground corn cobs, ground walnut shells, ground peanut hulls, and the like. If desired, the impregnated granulated absorbent carrier can be coated with a coating that will preserve the integrity of the granular until it is applied to an object or situs favorable for release of the active ingredient.

The rates of application to insects, mites, objects, or situs will depend upon the species of insects or mites to be controlled, the presence or absence of desirable living organisms, temperature conditions of treatment, and the method and efficiency of application. In general, insecticidal and miticidal activity is obtained when the compounds are applied at concentrations of about 10 to about 6000 ppm, perferably at concentrations of about 30 to about 4000 ppm.

The compositions containing benzoyl chloride phenylhydrazones according to the invention, can be applied to insects, mites, objects or situs by conventional methods. For example, an area of soil, a building, or plants can be treated by spraying wettable powder suspensions, emulsions, or solutions from power sprayers or from hand-operated knapsack sprayers. Dips can be used for livestock. Dusts can be applied by power dusters, or by hand-operated dusters. Creams and ointment formulations can be applied to skin or objects for prolonged protection from insects or mites.

The active compounds of the invention can also be formulated in relatively dilute proportions in a dispersible insecticide carrier for household applications. Thus, the active compounds can be formulated in dusts having from about 0.1 to 5.0% active ingredient with a dusting powder as hereinbefore described, and in solutions containing from about 0.01 to about 5.0% active ingredient with deodorized kerosene for aerosol applications.

It will of course be appreciated that the conditions encountered when applying the method and compositions of this invention to actual practice can vary widely. Included among the variables that may be encountered are the degree of infestation by insects or mites, the particular pest to be controlled, the particular situs being treated, the age or degree of development of animals or plants, the prevailing weather conditions, such as temperature. relative humidity, rainfall, dews, and so forth.

The compounds of Formula l are effective pesticides that can be used to control invertebrate pests in agriculture, in industry, and around the home. The compounds have been found to be active against invertebrate animals of the Phylum Arthropoda, illustratively Class Insecta, for example, order Coleoptera, more specifically, the cotton boll weevil (Anthonomus grandis Boheman). the confused flour beetle (Tribolium confusum Jacquelin de Val), and the Mexican bean beetle (Epilachna varii'estis Mulsant), order Diptera, more specifically, the housefly (Musca domestir'a Linnaeus), order Orthoptera, more specifically, the house cricket (Ar-hem domesticus Linnaeus), and the German cockroach (Blutella germanica Linnaeus), and order Lepidoptera, more specifically, the Southern armyworm (Prodenia eridania Cramer), and Class Arachnida, for example, order Acarina, more specifically, the two-spotted spider mite (Tetranychus urticae Koch).

Efficacy against invertebrate pests has been demonstrated at concentrations of 1000, 500, 100, 50, and even 10 ppm depending upon the specific insect or mite used. Some invertebrate animal pests will be more sensitive to the compounds than others, and others might be quite resistant. In general, the compounds of Formula I are used at concentrations ranging from about 30 to about 6000 ppm.

Compounds of the invention have also shown activity as defoliants and against parasitic worms, e.g., Nemataspiroides dubius and Syphacia obvelata. The compounds benzoyl chloride (2,5-dichlorophenyl)hydrazone and p-chlorobenzoyl chloride (2,4,6-trichlorophenyl)hydrazone have been found to have anorexigenic activity.

We'claim:

1. A composition for combating pestiferous insects and mites comprising a dispersible, solid carrier and a benzoyl chloride phenylhydrazone in effective amound having the structural formula:

wherein X is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; Y is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; n is an integer from 0 to 5, inclusive; and m is an integer from 0 to 3, inclusive; the sum of n m being not more than 6, the sum of carbon atoms in alkyl substituents being not more than l5, and there being no more than one nitro group in the molecule.

2. The composition according to claim 1 wherein the composition comprises one or more surface active agents.

' 3. The composition according to claim 2 for combating insects and mites comprising the specific compound benzoyl chloride phenylhydrazone.

4. THe composition according to claim 2 for combating insects and mites comprising the specific compound p-chlorobenzoyl chloride phenylhydrazone.

5. The composition according to claim 1 wherein m is 3 and Y is halogen.

6. The composition according to claim 5 wherein n is zero and Y is chlorine.

7. The composition according to claim 6 for combating insects and mites comprising the specific compound benzoyl chloride (2.4,6-trichlorophenyl)hydrazone.

8. The composition according to claim 1 wherein m is 2 and Y is halogen.

9. The composition according to claim 8 wherein n is zero and Y is chlorine.

10. The composition according to claim 9 for combating insects and mites comprising the specific compound benzoyl chloride (2.4-dichlorophenyl)hydrazone.

11. The composition according to claim 1 for comhating insects and mites comprising the specific compound pentafluorobenzoyl chloride phenylhydrazone.

12. The composition according to claim 2 wherein the dispersible carrier is a pulverulent solid.

13. A method of controlling insects and mites which comprises applying to a situs an insecticidal and miticidal amount of a benzoyl chloride phenylhydrazone having the structural formula:

wherein X is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; Y is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; n is an integer from 0 to 5, inclusive; and m is an integer from to 3. inclusive; the sum of n+m being not more than 6, the sum of carbon atoms in alkyl substituents being not more than l5, and there being no more than one nitro group in the molecule.

14. The method according to claim 13 wherein the specific compound benzoyl chloride phenylhydrazone is applied.

15. The method according to claim 13 wherein X is halogen, n is one, and m is zero.

16. The method according to claim 15 wherein X is p-chloro.

17. The method according to claim 15 wherein X is m-chloro.

18. The method according to claim 15 wherein X is p-bromo.

19. The method according to claim 15 wherein X is p-iodo.

20. The method according to claim 13 wherein the compound 3,4-dichlorobenzoyl chloride phenylhydrazone is applied.

21. The method according to claim 13 wherein the compound benzoyl chloride (2,5-dichlorophenyl)hydrazone is applied.

22. The method according to claim 13 wherein X is halogen, Y is halogen, and n and m each are one.

23. The method according to claim 22 wherein X is p-chloro and Y is p-bromo.

24. The method according to claim 13 wherein X is alkyl, n is one or two, and m is zero.

25. The method according to claim 24 wherein the compound 2,5-dimethylbenzoyl chloride phenylhydrazone is applied.

26. The method according to claim 24 wherein n is one and X is m-methyl.

27. The method according to claim 13 wherein Y is halogen and m is 3.

28. The method according to claim 27 wherein n is zero.

29. The method according to claim 28 wherein Y is chlorine.

30. The method according to claim 29 wherein the compound benzoyl chloride (2,4,6-trichlorophenyl)hydrazone is applied.

31. The method according to claim 13 wherein Y is halogen and m is 2.

32. The method according to claim 31 wherein n is zero.

33. The method according to claim 32 wherein Y is chlorine.

34. The method according to claim 33 wherein the compound benzoyl chloride (2,4-dichlorophenyl)hydrazone is applied.

35. The method according to claim 13 wherein X is halogen, and n is five.

36. The method according to claim 35 wherein the compound pentafluorobenzoyl chloride phenylhydrazone is applied. I

37. A method of controlling insects or mites which comprises contacting insects or mites with an insecticidal or miticidal, respectively, amount of a benzoyl chloride phenylhydrazone having the structural formula:

c (Y) I m C wherein X is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; Y is halogen, alkyl of from 1 to 6 carbon atoms, inclusive, and nitro; n is an integer from 0 to 5, inclusive; and m is an integer from 0 to 3, inclusive; the sum of n in being not more than 6, the sum of carbon atoms in alkyl substituents being not more than 15, and there being on more than one nitro group in the molecule.

38. The method according to claim 37 wherein the specific compound benzoyl chloride phenylhydrazone is applied.

39. The method according to claim 37 wherein X is halogen, n is one, and m is zero.

40. The method according to claim 39 wherein X is p-chloro.

41. The method according to claim 39 wherein X is m-chloro.

42. The method according to claim 39 wherein X is p-bromo.

43. The method according to claim 39 wherein X is p-iodo.

44. The method according to claim 37 wherein the compound 3,4-dichlorobenzoyl chloride phenylhydrazone is applied.

45. The method according to claim 37 wherein the compound benzoyl chloride (2.5-dichlorophenyl)hydrazone is applied.

46. The method according to claim 37 wherein X is halogen, Y is halogen. and n and In each are one.

47. The method according to claim 46 wherein X is p-chloro and Y is p-bromo.

48. The method according to claim 37 wherein X is alkyl, n is one or two, and m is zero.

49. The method according to claim 48 wherein the compound 2,5-dimethylbenzoyl chloride phenylhydrazone is applied.

50. The method according to claim 48 wherein n is one and X is m-methyl.

51. The method according to claim 37 wherein Y is 59. The method according to claim 37 wherein X is halogen, and n is five.

60. The method according to claim 59 wherein the compound pentafluorobenzoyl chloride phenylhydrazone is applied.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5,879,543 DATED April 22, 1975 INVENTOR(S) G i rts Kauga rs and Edw in G. Gemr ich, I I

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, l ine 15, for "initicidal' read miticidal Col umn 5, l ine 15, for "chromatogrph ic" read ch romatograph ic Column i, l ine 10, for "Preparation ll Benzoic acid (2,5-dichlorophenyl )hydrazide" read i ine 55, for

" read Analysis: Column 5, l ine 1 for "C, 47.92" read C, 47.95 l ine 2 for "(0.02 mole read (0.20 mole) Column 7, l ine 50, for "C, l6. i7" read C, i6.17 Column 10, l ine 55, for 0.015 read 0.105

Column 11, l ine 58, for "has" read had Column 15, l ine 21, for "C H Cl N read C H Cl N l ine 50, for o-tolyhydrazide" read o-tolylhydrazide Column l -l, l ine 55, For "Follwing" read Following Column 16, l ine 8, for "chlorde" read chloride l ine 15, for

read Analysis: Column 18, l ine 10, For cl, 55.69" read Cl, 55.69 Column 19, l ine 51, for "inclue" read include Column 22, l ine 50, claim 1, for "amound" read amount Column 24, l ine 60, cla im 57, for on read no Signed and Scaled this fourth Day Of No veniber 19 75 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Office Commissioner oflarems and Trademarks 

1. A composition for combating pestiferous insects and mites comprising a dispersible, solid carrier and a benzoyl chloride phenylhydrazone in effective amound having the structural formula:
 1. A COMPOSITION FOR COMBATING PESTIFEROUS INSECTS AND MITES COMPRISING A DISPERSIBLE, SOLID CARRIER AND A BENZOYL CHLORIDE PHENYLHYDRAZONE IN EFFECTIVE AMOUNT HAVING THE STRUCTURAL FORMULA:
 2. The composition according to claim 1 wherein the composition comprises one or more surface active agents.
 3. The composition according to claim 2 for combating insects and mites comprising the specific compound benzoyl chloride phenylhydrazone.
 4. THe composition according to claim 2 for combating insects and mites comprising the specific compound p-chlorobenzoyl chloride phenylhydrazone.
 5. The composition according to claim 1 wherein m is 3 and Y is halogen.
 6. The composition according to claim 5 wherein n is zero and Y is chlorine.
 7. The composition according to claim 6 for combating insects and mites comprising the specific compound benzoyl chloride (2,4, 6-trichlorophenyl)hydrazone.
 8. The composition according to claim 1 wherein m is 2 and Y is halogen.
 9. The composition according to claim 8 wherein n is zero and Y is chlorine.
 10. The composition according to claim 9 for combating insects and mites comprising the specific compound benzoyl chloride (2,4-dichlorophenyl)hydrazone.
 11. The composition according to claim 1 for combating insects and mites comprising the specific compound pentafluorobenzoyl chloride phenylhydrazone.
 12. The composition according to claim 2 wherein the dispersible carrier is a pulverulent solid.
 13. A method of controlling insects and mites which comprises applying to a situs an insecticidal and miticidal amount of a benzoyl chloride phenylhydrazone having the structural formula:
 14. The method according to claim 13 wherein the specific compound benzoyl chloride phenylhydrazone is applied.
 15. The method according to claim 13 wherein X is halogen, n is one, and m is zero.
 16. The method according to claim 15 wherein X is p-chloro.
 17. The method according to claim 15 wherein X is m-chloro.
 18. The method according to claim 15 wherein X is p-bromo.
 19. The method according to claim 15 wherein X is p-iodo.
 20. The method according to claim 13 wherein the compound 3,4-dichlorobenzoyl chloride phenylhydrazone is applied.
 21. The method according to claim 13 wherein the compound benzoyl chloride (2,5-dichlorophenyl)hydrazone is applied.
 22. The method according to claim 13 wherein X is halogen, Y is halogen, and n and m each are one.
 23. The method according to claim 22 wherein X is p-chloro and Y is p-bromo.
 24. The method according to claim 13 wherein X is alkyl, n is one or two, and m is zero.
 25. The method according to claim 24 wherein the compound 2,5-dimethylbenzoyl chloride phenylhydrazone is applied.
 26. The method according to claim 24 wherein n is one and X is m-methyl.
 27. The method according to claim 13 wherein Y is halogen and m is
 3. 28. The method according to claim 27 wherein n is zero.
 29. The method according to claim 28 wherein Y is chlorine.
 30. The method according to claim 29 wherein the compound benzoyl chloride (2,4,6-trichlorophenyl)hydrazone is applied.
 31. The method according to claim 13 wherein Y is halogen and m is
 2. 32. The method according to claim 31 wherein n is zero.
 33. The method according to claim 32 wherein Y is chlorine.
 34. The method according to claim 33 wherein the compound benzoyl chloride (2,4-dichlorophenyl)hydrazone is applied.
 35. The method according to claim 13 wherein X is halogen, and n is fivE.
 36. The method according to claim 35 wherein the compound pentafluorobenzoyl chloride phenylhydrazone is applied.
 37. A method of controlling insects or mites which comprises contacting insects or mites with an insecticidal or miticidal, respectively, amount of a benzoyl chloride phenylhydrazone having the structural formula:
 38. The method according to claim 37 wherein the specific compound benzoyl chloride phenylhydrazone is applied.
 39. The method according to claim 37 wherein X is halogen, n is one, and m is zero.
 40. The method according to claim 39 wherein X is p-chloro.
 41. The method according to claim 39 wherein X is m-chloro.
 42. The method according to claim 39 wherein X is p-bromo.
 43. The method according to claim 39 wherein X is p-iodo.
 44. The method according to claim 37 wherein the compound 3,4-dichlorobenzoyl chloride phenylhydrazone is applied.
 45. The method according to claim 37 wherein the compound benzoyl chloride (2,5-dichlorophenyl)hydrazone is applied.
 46. The method according to claim 37 wherein X is halogen, Y is halogen, and n and m each are one.
 47. The method according to claim 46 wherein X is p-chloro and Y is p-bromo.
 48. The method according to claim 37 wherein X is alkyl, n is one or two, and m is zero.
 49. The method according to claim 48 wherein the compound 2,5-dimethylbenzoyl chloride phenylhydrazone is applied.
 50. The method according to claim 48 wherein n is one and X is m-methyl.
 51. The method according to claim 37 wherein Y is halogen and m is
 3. 52. The method according to claim 51 wherein n is zero.
 53. The method according to claim 52 wherein Y is chlorine.
 54. The method according to claim 53 wherein the compound benzoyl chloride (2,4,6-trichlorophenyl)hydrazone is applied.
 55. The method according to claim 37 wherein Y is halogen and m is
 2. 56. The method according to claim 55 wherein n is zero.
 57. The method according to claim 56 wherein Y is chlorine.
 58. The method according to claim 57 wherein the compound benzoyl chloride (2,4-dichlorophenyl)hydrazone is applied.
 59. The method according to claim 37 wherein X is halogen, and n is five. 